US2640834A - Dithiocarbamates and derivatives thereof - Google Patents
Dithiocarbamates and derivatives thereof Download PDFInfo
- Publication number
- US2640834A US2640834A US742448A US74244847A US2640834A US 2640834 A US2640834 A US 2640834A US 742448 A US742448 A US 742448A US 74244847 A US74244847 A US 74244847A US 2640834 A US2640834 A US 2640834A
- Authority
- US
- United States
- Prior art keywords
- sulfolanyl
- dithiocarbamate
- thiolane
- water
- ethyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000012990 dithiocarbamate Substances 0.000 title description 32
- 150000004659 dithiocarbamates Chemical class 0.000 title description 4
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 18
- 239000000126 substance Substances 0.000 description 16
- CSNJTIWCTNEOSW-UHFFFAOYSA-N carbamothioylsulfanyl carbamodithioate Chemical compound NC(=S)SSC(N)=S CSNJTIWCTNEOSW-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- -1 sulfolanyl group Chemical group 0.000 description 15
- 239000011734 sodium Substances 0.000 description 14
- 229910052708 sodium Inorganic materials 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 9
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical class [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 9
- 229920001971 elastomer Polymers 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 239000005060 rubber Substances 0.000 description 6
- QDHHCQZDFGDHMP-UHFFFAOYSA-N Chloramine Chemical compound ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229940083608 sodium hydroxide Drugs 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- MBDNRNMVTZADMQ-UHFFFAOYSA-N sulfolene Chemical compound O=S1(=O)CC=CC1 MBDNRNMVTZADMQ-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 3
- 229960001763 zinc sulfate Drugs 0.000 description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- DROVFJSAGGLUJN-UHFFFAOYSA-N n-butyl-1,1-dioxothiolan-3-amine Chemical compound CCCCNC1CCS(=O)(=O)C1 DROVFJSAGGLUJN-UHFFFAOYSA-N 0.000 description 2
- BNVNYCSJNTUPFM-UHFFFAOYSA-N n-ethyl-1,1-dioxothiolan-3-amine Chemical compound CCNC1CCS(=O)(=O)C1 BNVNYCSJNTUPFM-UHFFFAOYSA-N 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000013040 rubber vulcanization Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- 229960002447 thiram Drugs 0.000 description 2
- 238000001665 trituration Methods 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- POJSXHDVRJSEOP-UHFFFAOYSA-N 1,1-dioxo-n-propylthiolan-3-amine Chemical compound CCCNC1CCS(=O)(=O)C1 POJSXHDVRJSEOP-UHFFFAOYSA-N 0.000 description 1
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 1
- ILNGCUVXLQVDTC-UHFFFAOYSA-N 4-chloromorpholine Chemical compound ClN1CCOCC1 ILNGCUVXLQVDTC-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 244000024893 Amaranthus tricolor Species 0.000 description 1
- 235000014748 Amaranthus tricolor Nutrition 0.000 description 1
- LQVXSNNAFNGRAH-QHCPKHFHSA-N BMS-754807 Chemical compound C([C@@]1(C)C(=O)NC=2C=NC(F)=CC=2)CCN1C(=NN1C=CC=C11)N=C1NC(=NN1)C=C1C1CC1 LQVXSNNAFNGRAH-QHCPKHFHSA-N 0.000 description 1
- CAHQGWAXKLQREW-UHFFFAOYSA-N Benzal chloride Chemical compound ClC(Cl)C1=CC=CC=C1 CAHQGWAXKLQREW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 244000304337 Cuminum cyminum Species 0.000 description 1
- 235000007129 Cuminum cyminum Nutrition 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- NPPQSCRMBWNHMW-UHFFFAOYSA-N Meprobamate Chemical compound NC(=O)OCC(C)(CCC)COC(N)=O NPPQSCRMBWNHMW-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 235000010725 Vigna aconitifolia Nutrition 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- FQNGWRSKYZLJDK-UHFFFAOYSA-N [Ca].[Ba] Chemical compound [Ca].[Ba] FQNGWRSKYZLJDK-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- DRCRQRUTHVDZPF-UHFFFAOYSA-L barium(2+) dicarbamodithioate Chemical compound C(N)([S-])=S.[Ba+2].C(N)([S-])=S DRCRQRUTHVDZPF-UHFFFAOYSA-L 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- GNVMUORYQLCPJZ-UHFFFAOYSA-N carbamothioic s-acid Chemical compound NC(S)=O GNVMUORYQLCPJZ-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- NIAUYOOLQHAXNR-UHFFFAOYSA-N n-benzyl-1,1-dioxothiolan-3-amine Chemical compound C1S(=O)(=O)CCC1NCC1=CC=CC=C1 NIAUYOOLQHAXNR-UHFFFAOYSA-N 0.000 description 1
- TYDFLVGVWMSQAC-UHFFFAOYSA-N n-chloro-n-ethylethanamine Chemical compound CCN(Cl)CC TYDFLVGVWMSQAC-UHFFFAOYSA-N 0.000 description 1
- HSPSCWZIJWKZKD-UHFFFAOYSA-N n-chloroacetamide Chemical compound CC(=O)NCl HSPSCWZIJWKZKD-UHFFFAOYSA-N 0.000 description 1
- SJGFVFYSANQLLE-UHFFFAOYSA-N n-chlorocyclohexanamine Chemical compound ClNC1CCCCC1 SJGFVFYSANQLLE-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 150000003558 thiocarbamic acid derivatives Chemical class 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 125000001166 thiolanyl group Chemical group 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- MBBWTVUFIXOUBE-UHFFFAOYSA-L zinc;dicarbamodithioate Chemical compound [Zn+2].NC([S-])=S.NC([S-])=S MBBWTVUFIXOUBE-UHFFFAOYSA-L 0.000 description 1
- IPSRAFUHLHIWAR-UHFFFAOYSA-N zinc;ethane Chemical group [Zn+2].[CH2-]C.[CH2-]C IPSRAFUHLHIWAR-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/46—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings substituted on the ring sulfur atom
- C07D333/48—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings substituted on the ring sulfur atom by oxygen atoms
Definitions
- T is the sulfolanyl group Patented June 2, 1953 UNITED STATES PATENT OFFICE DITHIOCARBAMATES AND DERIVATIVE S THEREOF Lyndon B. Tewksbury, Jr., Potsdam, N. Y., and Sylvia St Heikkila, Naugatuck, Conn., assignors to United States Rubber Company, New York, N. Y., a corporation of New Jersey No Drawing. Application April 18, 1947,
- R is a functionally aliphatic group
- R is a thiolane nucleus.
- it relates 1 to the metal salts of a thiocarbamic acid having the formula i R s N--C-S-Na ⁇ N(IS-H r H a 2 R and R1 being as defined.
- H2 1 An object of the invention is to provid a new series of chemicals.
- a further object is to provide chemicals which may be used in the manufacture
- Examples of functionally aliphatic substituents of rubber goods derived from natural or synthetic epresented by a methyl ethy?) n'propyl rubber which includes the polybutadienes, polylsopmpyl' lsobutyl' lsoamyl substituted butadienes, and modified polybutaclohexyli beltzyli anyl' methanyl n'octyL dienes, such as GRS and GRA.
- Another object 5 decyl: substltuted'alkyls' for example beta” is to provide chemicals which may be used as 2 methoxy ethyl betachlqroethyl' rubber vulcanization accelerators, or as lubricant of the Various l thlo' oil additives, or as intermediates in the preparalanes whlch may be reacted Wlth carbon dlsulfide tion of other chemicals.
- Other objects will be and base a apparent from the hereinafter description.
- 1,1-dioxo 3-methy1amino thiolane The chemicals may be prepared from a second- 1,1-di0x0 3-ethy1amino thiolane ary amine having the formula 1,1-dioxo 3-n-propylamino thiolane H 3-cyclohexylamino 1,1-dioxothio1ane A N- T 3-benzylamino 1,1-dioxo thiolane 3-allylamino 1,1-dioxo thiolane 1,1-dioxo 3-methallylamino thiolane 1,1-di0xo 3-isopropylamino thiolane H 1,1-dioxo 3-dodecy1amino thiolane n 1,1-dioxo 3-,8-methoxyethylamino thiolane.
- the corresponding salts of the following are also within the scope of the invention: potassium, ammooi nium (hypothetical metal) and substituted amby reacting the amine with carbon disulfide and momum' coppel? magnes.mm cadm.1um an alkali, whereby to form the water-soluble 4 mercury Fhrommm manganese lrgm alkali-metal dithiocarbamates.
- Other metal cobalt mckeliselfzmum
- the salts such as those of calcium barium, iron, lead, Soluble i partlculaljly t Zmc and lead Salts etc., may be derived from the alkali-metal diare effecplvt?
- thiocarbamates e. g., from sodium dithiocar-
- the dlthmmbamste salts may be converjted bamate, by replacing the alkali-metal by reaction 5 to .esters by lzeactmg w broadly Varlous with a solution of the metal which is desired to hahdes such replace the sodium.
- 4-nitrochloro benzene The secondary amine may be prepared from ZA-dinitrochloro benzene butadiene sulfone and the appropriate aliphatic Triphenyl methyl chloride primary amine by heating the two together, e. '55 Benzal chlorid where A is a functionally aliphatic radical, and
- the dithiocarbamates may also be reacted with so-called positive chlorine compounds such as:
- S N-ethyl N-sulfolanyl-3 thiocarbamyl
- S indicates that the thiocarbamyl group is joined to the sulfur of the sulfenamide (SNI-Iz) nucleus.
- SNI-Iz sulfur of the sulfenamide
- the sulfen-amides may conform to either the depending on the type of positive chlorine compound used.
- N-chlorcyclohexylamine is reacted with an alkali-metal salt, the reaction is. illustrated as follows:
- N-chlor diethylamine is used
- the corresponding end product is of the type R S ethyl Nt 1 s N/ ethyl
- N-chlor acetamide is used
- the end product is of the type Where N-chlor morpholine is used
- the end product is of the type NttS n CH2CH2
- thiuram disulfides formed by oxidation of the dithiocarbamate with iodine, chlorine, sodium hypochlorite, acidified hydrogen peroxide, etc.
- Exemplary of useful thiuram disulfides are:
- Example 2 --Potassium n-butyl sulfolanyZ-3-di- 'thiocarbamctte
- a mixture of 47.7 g. S-n-butylamino 1,1-dioxothiolane and 16.5 g. potassium hydroxide in 250 cc. water is stirred 4 hours at 10-15 C. with 16.2 g. carbon disulfide and the mixture filtered.
- the clear filtrate is an aqueous solution of the potassium salt of n-butyl sulfolanyl-3 dithiocarbamic acid.
- a crystalline material softening at 71-76 C. and decomposing at 87 C. is obtained.
- Example 3 Barz'um n-butyl sulfoZanyZ-3 d1- thiocarbamate
- An aqueous solution of sodium n-butyl sulfolany1-3 dithiocarbamate is mixed with an aqueous solution of barium chloride instoichiometric amounts.
- the barium dithiocarbamate precipitates. After Washing and drying it melts at 165-170 C. with decomposition.
- Example 4.Ferroas n-batyl salfolanyl-S dithiocarbamate This salt is prepared from ferrous sulfate and sodium n-butyl sulfolanyl-3 dithiocarbamate in Water solution. Precipitation occurs immediately. The dark brown salt after drying melts with decomposition beginning around 140 C.
- Example 5(a) .1,1-dtoxo-3-ethylamino thiolane Butadiene sulfone (A g.) and 90 cc. of a 70% aqueous solution of ethylamine are heated 5% hours at 6570 C. in a thick walled flask. The unreacted ethylamine and water are removed in a vacuum from a Water bath at approximately -50 C. An oil amounting to g. and consisting of 1,1-dioxo-3-ethylamino thiolane is ob- .tained.
- Example 5 (b) .--Soclium ethyl sulfolanyl-3 dithiocarbamate Two tenths mol of the above amine is mixed with 33.3 cc. (0.2 mol) of 6 N sodiumhydroxide and 70 cc. water, and the mixture is cooled to 10 C. while 9.0 cc. carbon disulfide are added slowly with stirring.
- Example 6 Zinc ethyl sulfolanyl-3 dithiocarbamate On treatment of a water solution of sodium ethyl sulfo1anyl-3 dithiocarbamate with an equivalent amount of zinc sulfate, a yellow precipitate immediately forms which is filtered, washed, and
- Example 7 S (N -ethyl N -sulfolanyl-3 thiocarbamyl) sulfe'namide A water solution containing 0.2 mol of the sodium salt of the dithiocarbamate of Example 5 is treated at 05 C. With a slight excess of monochloramine solution. The product after filtration and washing with water is recrystallized from alcohol. An 80% yield of S-(N-ethy1-l I'- sulfolanyl-B thiocarbamyl) sulfenamide melting 103-5" C. is obtained.
- Example 8(a) .-1,1-clioxo 3-allylamino thiolane Butadiene sulfone (59 g.), allylamine (114 g.) and 114 cc. water are heated in a thick-walled flask 10 hours at 70 C. The unreacted amine and Water are removed under vacuum from a water bath at 40-50" C. The oily residue consisting of 1,1-dioxo 3-allylamino thiolane amounts to 73.4 g.
- Example 8(b) -Sodium allyl sulfolanyl-B' dithiocarbamate
- 8 g. sodium hydroxide in 200 cc. water and 7.6 g. carbon d1- sulfide After 1 /2 hours stirring, an orange solution of sodium allyl su1folanyl-3 dithiocarbamate is obtained.
- Example 9 S (N -allyl-N-sulfolany'l-3' thiocarbamyl) salfenamzde
- the dithiocarbamate solution of Example 8 is treated with excess monochloramine as previously described.
- S-(N'-allyl-N' sulfolanyl 3 thiocarbamyl) sulfenamide is obtained as a white powder of melting range -86 C.
- Example 10 Zinc allyl suzfbzanyz-a dithiocarbamate
- the dithiocarbamate solution of Example 8 is mixed with an equivalent amount of zinc sulfate. There immediately precipitates the corresponding insoluble zinc dithiocarbamate. 1
- Example 1 1 .S-' (N -butyl-N -salfolanyl-3- thiocarbamyl) salfenamide This material having a-melting range of 72-76 C. is prepared from monochloramine and sodium butyl sulfo1anyl-3-dithiocarbamate of Example 1.
- Example 12.--S0diam methyl salfolanyl-3 dithiocarbamate Thirty grams 1,1-dioxo 3-methyl amino thiolane are converted to the dithiocarbamate with 8 g. sodium hydroxide and 10.8 cc. carbon disulfide in 200 cc. water at 10-15" C.
- Example 13 --Bis (methyl sulfolanyl-3) thiuram disulfide
- the dithiocarbamate solution of Example 12 is diluted to 500 cc. and cooled to 0-5 C. At this temperature it is treated with asolution of 11 g. 30% hydrogen peroxideand 9.8 g. sulfuric acid in 35 cc. Water. The product which precipitates during the peroxide addition is filtered, washed with water and dried. After digestion with alcohol, 31.8 g. bis (N-methyl-N-sulfolanyl- 3) thiuram disulfide melting 172-175 C. with decomposition are obtained.
- Example 14.-B2's (ethyl salfolanyl-) thiuram disulfide The aqueous solution of sodium ethyl sulfolanyl-3 dithiocarbamate (0.2 mol) (Example 5) is diluted to three times its volume (approximately 300 cc.) cooled to below 5 C., and treated with 0.1 mol iodine as an aqueous potassium iodide complex solution. After standing overnight, the white product is filtered, washed with water, and dried. A yield amounting to- 73% of his (ethyl sulfolanyl-B) thiuram disulfide as a white powder melting 162-16 9 C. is obtained.
- Example 15 S-(N-methyl-N-sulfolanyl-3 thiocarbamyl) sulfenamide A dithiocarbamate solution prepared according to Example 12 is treated with monochloramine. The product after filtration and washing with Water melts hi l- C.
- Example 16 Zinc n-batyl sulfolanyl-B dithiocarbamate This zinc salt is obtained as a white powder by treating the sodium salt of the dithiocarbamate (Example 1) with the calculated amount of zinc sulfate.
- Example 17 --Ethyl sulfolanylammonium salt of ethyl salfoZanyl-3 aithz'oecarbamic acid
- a cold solution of (34.2 g.) 1,1-dioxo 3-ethylamino thiolane in 75 cc. ether a solution of 6.02 cc. carbon disulfide in 15 cc. of ether is added. After stirring for several hours a viscous oil consisting of ethyl su1folany1-3 ammonium ethyl su1fo1any1-3 dithiocarbamate separates.
- Example 18 The various chemicals of this invention are Chemical I-S-(N-ethyl-N'-su1folany1-3 thiocarbamyl) sulfenamide Chemical IIBis (ethyl 'su1fo1anyl-3) thiuram disulfide Chemical IIIS-'(N'-methyl 1N sulfolanyl-3 thiocarbamyl.) sulfenamide Chemical IV-Zinc n-butyl su'lfolanyl-3 dithiocarbamate Stock Above Master Batch Chemical :1 Chemical II Chemical III Chemical IV...-
- the various stocks are cured 30, 45, 60, and 90 minutes "at 45 pounds per square inch steam pressure.
- Compounds or other conventional vulcanizable compounds of natural or synthetic rubbers are herein considered equivalent to rubber, examples being the Buna types (polymers essentially derived from butadiene-1,3) such as Buna N (rubbery copolymer of butadiene-1,3 and acrylonitrile) and Buna S (rubbery copolymer of butadiene-1,3 and styrene).
- Buna types polymers essentially derived from butadiene-1,3
- Buna S rubbery copolymer of butadiene-1,3 and styrene
- sulfur In place of sulfur, other conventional vulcanizing agents susceptible to acceleration may be included.
- the accelerators may, if desired, be employed with conventional accelerator activators used with other known accelerators. Also, the new accelerators may be used in combination with known accelerators such as diphenyl guanidine, or conventional thiazyl sulfide accelerators, such as mercaptobenzothiazole and dibenzothiazyl sulfide, etc.
- the proportion of the accelerators is the same as the proportion used with other conventional accelerators in the vulcanization of the various elastomers.
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Description
' T is the sulfolanyl group Patented June 2, 1953 UNITED STATES PATENT OFFICE DITHIOCARBAMATES AND DERIVATIVE S THEREOF Lyndon B. Tewksbury, Jr., Potsdam, N. Y., and Sylvia St Heikkila, Naugatuck, Conn., assignors to United States Rubber Company, New York, N. Y., a corporation of New Jersey No Drawing. Application April 18, 1947,
Serial No. 742,448
1 Claim. (01. 260-3321) 1 2 This invention relates to dithiocarbamates and 5-24 hours at a mildly elevated temperature such derivatives containing the essential N-substituted as 50-80 C. Butadiene sulfone thiocarbamyl sulfide group CH-CH R\ %S 5 (so: OHrCH R is prepared from reacting sulfur dioxide with butadiene-1,3.
In the case of sodium alkyl sulfolanyl-S dithiocarbamate, the formula would be where R is a functionally aliphatic group, and R is a thiolane nucleus. In particular, it relates 1 to the metal salts of a thiocarbamic acid having the formula i R s N--C-S-Na \N(IS-H r H a 2 R and R1 being as defined. H2 1 An object of the invention is to provid a new series of chemicals. A further object is to provide chemicals which may be used in the manufacture Examples of functionally aliphatic substituents of rubber goods derived from natural or synthetic epresented by a methyl ethy?) n'propyl rubber, which includes the polybutadienes, polylsopmpyl' lsobutyl' lsoamyl substituted butadienes, and modified polybutaclohexyli beltzyli anyl' methanyl n'octyL dienes, such as GRS and GRA. Another object 5 decyl: substltuted'alkyls' for example beta" is to provide chemicals which may be used as 2 methoxy ethyl betachlqroethyl' rubber vulcanization accelerators, or as lubricant of the Various l thlo' oil additives, or as intermediates in the preparalanes whlch may be reacted Wlth carbon dlsulfide tion of other chemicals. Other objects will be and base a apparent from the hereinafter description. 1,1-dioxo 3-methy1amino thiolane The chemicals may be prepared from a second- 1,1-di0x0 3-ethy1amino thiolane ary amine having the formula 1,1-dioxo 3-n-propylamino thiolane H 3-cyclohexylamino 1,1-dioxothio1ane A N- T 3-benzylamino 1,1-dioxo thiolane 3-allylamino 1,1-dioxo thiolane 1,1-dioxo 3-methallylamino thiolane 1,1-di0xo 3-isopropylamino thiolane H 1,1-dioxo 3-dodecy1amino thiolane n 1,1-dioxo 3-,8-methoxyethylamino thiolane.
In addition to the sodium salts, the corresponding salts of the following are also within the scope of the invention: potassium, ammooi nium (hypothetical metal) and substituted amby reacting the amine with carbon disulfide and momum' coppel? magnes.mm cadm.1um an alkali, whereby to form the water-soluble 4 mercury Fhrommm manganese lrgm alkali-metal dithiocarbamates. Other metal cobalt mckeliselfzmum and The salts such as those of calcium barium, iron, lead, Soluble i partlculaljly t Zmc and lead Salts etc., may be derived from the alkali-metal diare effecplvt? as vulcamzatlon accelerators thiocarbamates, e. g., from sodium dithiocar- The dlthmmbamste salts may be converjted bamate, by replacing the alkali-metal by reaction 5 to .esters by lzeactmg w broadly Varlous with a solution of the metal which is desired to hahdes such replace the sodium. 4-nitrochloro benzene The secondary amine may be prepared from ZA-dinitrochloro benzene butadiene sulfone and the appropriate aliphatic Triphenyl methyl chloride primary amine by heating the two together, e. '55 Benzal chlorid where A is a functionally aliphatic radical, and
The dithiocarbamates may also be reacted with so-called positive chlorine compounds such as:
Monochloramine (NHz- C1) N-chlorcyclohexylamine N-chlorpiperidine N-chlor acetamide N-chlor succinamide N-chlor di n-butylamine N-chlor diethylamine N-chlor morpholine N-chlor isopropylamine N-chlor diamylamine to form sulfenamide type compounds by a procedure as illustrated in Examples 7, 9, 11, and 15 below. Example? below describes the preparation of S (N-ethyl N-sulfolanyl-3 thiocarbamyl) sulfenamide, having the formula In the name, S indicates that the thiocarbamyl group is joined to the sulfur of the sulfenamide (SNI-Iz) nucleus. To differentiate between the nitrogens, the thiocarbamyl nitrogen is labeled N as indicated.
The sulfen-amides may conform to either the depending on the type of positive chlorine compound used. For example, where N-chlorcyclohexylamine is reacted with an alkali-metal salt, the reaction is. illustrated as follows:
Where N-chlor diethylamine is used, the corresponding end product is of the type R S ethyl Nt 1 s N/ ethyl Where N-chlor acetamide is used, the end product is of the type Where N-chlor morpholine is used, the end product is of the type NttS n CH2CH2 Of particular value, are the thiuram disulfides formed by oxidation of the dithiocarbamate with iodine, chlorine, sodium hypochlorite, acidified hydrogen peroxide, etc. Exemplary of useful thiuram disulfides are:
Bis (methyl sulfolanyl-B) thiuram disulfide Bis (ethyl sulfolanyl-B) thiuram disulfide Bis (n-propyl sulfolanyl-B) thiuram disulfide Bis (n-butyl sulfolanyl-3) thiuram disulfide Bis (n-amyl sulfolanyl-3) thiuram disulfide Bis (n-octyl sulfolanyl-3) thiuram disulfide Bis (n-dodecyl sulfolanyl-3) thiuram disulfide Bis (isopropyl sulfolanyl-3) thiuram disulfide Bis (isobutyl sulfolanyl-3) thiuram disulfide Bis (isoamyl sulfolanyl-S) thiuram disulfide The following examples are given to illustrate the preparation of the chemicals, the parts being by weight:
Example 1(a).1,1-diomo-3-n-butylamino thiolane 1,1-dioxothiolane-3 (butadiene sulfone) 59 g., 146 g. n-butylamine and 146 cc. water are heated at 65-70 C. for 13% hours in a flask equipped with a reflux condenser. The unreacted amine and most of the water are removed in a good vacuum from a water bath at approximately 40-50 C. The oily residue weighs 97.3 g. The theoretical yield of 1,1-dioxo-3-n-butylamino thiolane is 95.5 g., indicating the presence of a small amount of water.
Example 1(b).-Sodium n-butyl suZjoZanyl-S- dithiocarbamate A mixture of 47.7 g. 1,1-dioxo 3-n-butylamino thiolane and 10.0 g. sodium hydroxide in 250 cc. water is treated in an ice bath with stirring with 16.2 g. carbon disulfide. After 3 hours stirring, an orange solution of sodium n-butyl sulfolanyl-B dithiocarbamate is obtained. By evaporation under reduced pressure, a heavy oil is obtained, which solidified on trituration with acetone. The white crystalline solid softens at -100 C. and decomposes at 128 C.
Example 2.--Potassium n-butyl sulfolanyZ-3-di- 'thiocarbamctte A mixture of 47.7 g. S-n-butylamino 1,1-dioxothiolane and 16.5 g. potassium hydroxide in 250 cc. water is stirred 4 hours at 10-15 C. with 16.2 g. carbon disulfide and the mixture filtered. The clear filtrate is an aqueous solution of the potassium salt of n-butyl sulfolanyl-3 dithiocarbamic acid. By evaporation under reduced pressure and trituration with alcohol, a crystalline material softening at 71-76 C. and decomposing at 87 C. is obtained.
Example 3.-Barz'um n-butyl sulfoZanyZ-3 d1- thiocarbamate An aqueous solution of sodium n-butyl sulfolany1-3 dithiocarbamate is mixed with an aqueous solution of barium chloride instoichiometric amounts. The barium dithiocarbamate precipitates. After Washing and drying it melts at 165-170 C. with decomposition.
Example 4.Ferroas n-batyl salfolanyl-S dithiocarbamate This salt is prepared from ferrous sulfate and sodium n-butyl sulfolanyl-3 dithiocarbamate in Water solution. Precipitation occurs immediately. The dark brown salt after drying melts with decomposition beginning around 140 C.
Example 5(a) .1,1-dtoxo-3-ethylamino thiolane Butadiene sulfone (A g.) and 90 cc. of a 70% aqueous solution of ethylamine are heated 5% hours at 6570 C. in a thick walled flask. The unreacted ethylamine and water are removed in a vacuum from a Water bath at approximately -50 C. An oil amounting to g. and consisting of 1,1-dioxo-3-ethylamino thiolane is ob- .tained.
Example 5 (b) .--Soclium ethyl sulfolanyl-3 dithiocarbamate Two tenths mol of the above amine is mixed with 33.3 cc. (0.2 mol) of 6 N sodiumhydroxide and 70 cc. water, and the mixture is cooled to 10 C. while 9.0 cc. carbon disulfide are added slowly with stirring.
After 2 hours, a clear orange brown solution of the sodium ethyl sulfolanyl-3 dithiocarbamate is obtained.
Example 6.Zinc ethyl sulfolanyl-3 dithiocarbamate On treatment of a water solution of sodium ethyl sulfo1anyl-3 dithiocarbamate with an equivalent amount of zinc sulfate, a yellow precipitate immediately forms which is filtered, washed, and
dried.
Example 7 .S (N -ethyl N -sulfolanyl-3 thiocarbamyl) sulfe'namide A water solution containing 0.2 mol of the sodium salt of the dithiocarbamate of Example 5 is treated at 05 C. With a slight excess of monochloramine solution. The product after filtration and washing with water is recrystallized from alcohol. An 80% yield of S-(N-ethy1-l I'- sulfolanyl-B thiocarbamyl) sulfenamide melting 103-5" C. is obtained.
Analysis Theory Found 11. O 10. 64 i3if:::::i::jii:::ii:i 37.8 37.58
Example 8(a) .-1,1-clioxo 3-allylamino thiolane Butadiene sulfone (59 g.), allylamine (114 g.) and 114 cc. water are heated in a thick-walled flask 10 hours at 70 C. The unreacted amine and Water are removed under vacuum from a water bath at 40-50" C. The oily residue consisting of 1,1-dioxo 3-allylamino thiolane amounts to 73.4 g.
Example 8(b) .-Sodium allyl sulfolanyl-B' dithiocarbamate Thirty-five grams of 3-allylamino 1,1-d ox0 thiolane are treated in the cold with 8 g. sodium hydroxide in 200 cc. water and 7.6 g. carbon d1- sulfide. After 1 /2 hours stirring, an orange solution of sodium allyl su1folanyl-3 dithiocarbamate is obtained.
Example 9.'-S (N -allyl-N-sulfolany'l-3' thiocarbamyl) salfenamzde The dithiocarbamate solution of Example 8 is treated with excess monochloramine as previously described. S-(N'-allyl-N' sulfolanyl 3 thiocarbamyl) sulfenamide is obtained as a white powder of melting range -86 C.
Example 10.-Zinc allyl suzfbzanyz-a dithiocarbamate The dithiocarbamate solution of Example 8 is mixed with an equivalent amount of zinc sulfate. There immediately precipitates the corresponding insoluble zinc dithiocarbamate. 1
Example 1 1 .S-' (N -butyl-N -salfolanyl-3- thiocarbamyl) salfenamide This material having a-melting range of 72-76 C. is prepared from monochloramine and sodium butyl sulfo1anyl-3-dithiocarbamate of Example 1.
Example 12.--S0diam methyl salfolanyl-3 dithiocarbamate Thirty grams 1,1-dioxo 3-methyl amino thiolane are converted to the dithiocarbamate with 8 g. sodium hydroxide and 10.8 cc. carbon disulfide in 200 cc. water at 10-15" C.
Example 13.--Bis (methyl sulfolanyl-3) thiuram disulfide The dithiocarbamate solution of Example 12 is diluted to 500 cc. and cooled to 0-5 C. At this temperature it is treated with asolution of 11 g. 30% hydrogen peroxideand 9.8 g. sulfuric acid in 35 cc. Water. The product which precipitates during the peroxide addition is filtered, washed with water and dried. After digestion with alcohol, 31.8 g. bis (N-methyl-N-sulfolanyl- 3) thiuram disulfide melting 172-175 C. with decomposition are obtained.
Example 14.-B2's (ethyl salfolanyl-) thiuram disulfide The aqueous solution of sodium ethyl sulfolanyl-3 dithiocarbamate (0.2 mol) (Example 5) is diluted to three times its volume (approximately 300 cc.) cooled to below 5 C., and treated with 0.1 mol iodine as an aqueous potassium iodide complex solution. After standing overnight, the white product is filtered, washed with water, and dried. A yield amounting to- 73% of his (ethyl sulfolanyl-B) thiuram disulfide as a white powder melting 162-16 9 C. is obtained.
Example 15.S-(N-methyl-N-sulfolanyl-3 thiocarbamyl) sulfenamide A dithiocarbamate solution prepared according to Example 12 is treated with monochloramine. The product after filtration and washing with Water melts hi l- C.
Example 16.Zinc n-batyl sulfolanyl-B dithiocarbamate This zinc salt is obtained as a white powder by treating the sodium salt of the dithiocarbamate (Example 1) with the calculated amount of zinc sulfate.
Example 17.--Ethyl sulfolanylammonium salt of ethyl salfoZanyl-3 aithz'oecarbamic acid To a cold solution of (34.2 g.) 1,1-dioxo 3-ethylamino thiolane in 75 cc. ether, a solution of 6.02 cc. carbon disulfide in 15 cc. of ether is added. After stirring for several hours a viscous oil consisting of ethyl su1folany1-3 ammonium ethyl su1fo1any1-3 dithiocarbamate separates.
7 The following examples are given to illustrate the efiectiveness of the chemicals as rubber vulcanization accelerators, the parts being by weight:
Example 18 The various chemicals of this invention are Chemical I-S-(N-ethyl-N'-su1folany1-3 thiocarbamyl) sulfenamide Chemical IIBis (ethyl 'su1fo1anyl-3) thiuram disulfide Chemical IIIS-'(N'-methyl 1N sulfolanyl-3 thiocarbamyl.) sulfenamide Chemical IV-Zinc n-butyl su'lfolanyl-3 dithiocarbamate Stock Above Master Batch Chemical :1 Chemical II Chemical III Chemical IV...-
The various stocks are cured 30, 45, 60, and 90 minutes "at 45 pounds per square inch steam pressure.
Cumin Elongaiv Tensile Strength (p. s.-1.-) Minutes at tion,
45 Percent Stock A Stock B Stock 0 Stock D 300 10 950 310 030 500 1, 0 1,710 690 1,420 1 Break 2,120-660 2,350-040 1,1085-686 aosasss "s00 830 1,050 810 780 500 1 1,790 2,150 1,740 1, 780 Break 2,600-655 2,320-520 2,11a59s 2,010-503 300 950 1,115 900 900 500 1,010 2,:250 2, 010 1,040 Break; 2,-400-540 2, 550-526 2, 520-500 2, 570- 300 990 1, 200 1110 I 1, 015 500 2,200 2,400. 1900 1.11..." Break. assasss 2,-650-520, 2,-280-576 2,0154% The new accelerators are equally efiective in natural rubber tread compounds, and in latex;
"compounds or other conventional vulcanizable compounds of natural or synthetic rubbers. The various vulcanizable synthetic rubbers are herein considered equivalent to rubber, examples being the Buna types (polymers essentially derived from butadiene-1,3) such as Buna N (rubbery copolymer of butadiene-1,3 and acrylonitrile) and Buna S (rubbery copolymer of butadiene-1,3 and styrene). In place of sulfur, other conventional vulcanizing agents susceptible to acceleration may be included.
The accelerators may, if desired, be employed with conventional accelerator activators used with other known accelerators. Also, the new accelerators may be used in combination with known accelerators such as diphenyl guanidine, or conventional thiazyl sulfide accelerators, such as mercaptobenzothiazole and dibenzothiazyl sulfide, etc.
The proportion of the accelerators is the same as the proportion used with other conventional accelerators in the vulcanization of the various elastomers.
Other ratios of compounding ingredients other than those given in Example 18, as well as other desired fillers, pigments, softeners, antioxidants, and the like may be employed in the production of various types of rubber compounds, as will be apparent to those skilled in the art of vulcanization of rubber.
Having thus described our invention, what we claim and desire to protect by Letters Patent is:
A sulfenamide of the formula where R is an unsubstituted sulfolanyl-B group.
LYNDON B. TEWKSBURY, JR. SYLVIA .S. HEIKKILA.
References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,219,006 Delfs Oct. 22, 1940 2,285,813 Hanslick June 9, 1942 2,291,798 Deli Aug. '4, 1942 2,325,194 Olin July 27, 1943 2,333,468 Cooper Nov. 2, 1943 2,372,161 Morris Mar. 20, 1945 2,376,338 Browning May 22, 1945 2,381,392 Smith Aug. 7, 1945 2,396,789 Hunt Mar. '19, 1946 2,400,029 Somerville May 7, 1946 2,411,219 Mathes Nov. 19, 1946 2,424,921 Smith July 29, 1947 2,432,255 Skaptason Dec. 9, 1947 2,432,256 Skaptason Dec. 9, 1947 2,435,404 Morris Feb. '3, 1948 2,469,838 Morris May 10, 1949
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US3075003A (en) * | 1959-05-21 | 1963-01-22 | Int Flavors & Fragrances Inc | Terpene alcohol, ester thereof and process for making same |
US4459366A (en) * | 1982-09-30 | 1984-07-10 | Phillips Petroleum Company | Passivating metals on cracking catalysts |
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US2325194A (en) * | 1941-03-06 | 1943-07-27 | Sharples Chemicals Inc | Manufacture of organic polysulphides |
US2376338A (en) * | 1941-09-22 | 1945-05-22 | Goodrich Co B F | Polymerization of butadiene-1, 3 hydrocarbons |
US2424921A (en) * | 1943-05-26 | 1947-07-29 | Firestone Tire & Rubber Co | Thiocarbamyl sulfenamides |
US2381392A (en) * | 1943-05-26 | 1945-08-07 | Firestone Tire & Rubber Co | Vulcanization accelerator |
US2372161A (en) * | 1943-07-27 | 1945-03-20 | Shell Dev | Sulphurized amides and imides of cyclic sulphones |
US2435404A (en) * | 1943-11-27 | 1948-02-03 | Shell Dev | Hydrogenation of sulfolane ethers |
US2396789A (en) * | 1944-03-03 | 1946-03-19 | Du Pont | Esters |
US2400029A (en) * | 1944-04-20 | 1946-05-07 | Vanderbilt Co R T | Compounding and vulcanization of synthetic rubber |
US2411219A (en) * | 1944-12-02 | 1946-11-19 | Goodrich Co B F | Reaction products of dihaloethers with dithiocarbamates |
US2432255A (en) * | 1945-06-06 | 1947-12-09 | Us Rubber Co | Thiocarbamosulfenamides as fungicides |
US2469838A (en) * | 1946-10-28 | 1949-05-10 | Shell Dev | Sulfolanyl carbamates |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2810728A (en) * | 1951-10-25 | 1957-10-22 | British Celanese | Beta-sulphonyl ketones |
US3041352A (en) * | 1958-12-22 | 1962-06-26 | Shell Oil Co | Substituted polyamines |
US3075003A (en) * | 1959-05-21 | 1963-01-22 | Int Flavors & Fragrances Inc | Terpene alcohol, ester thereof and process for making same |
US4459366A (en) * | 1982-09-30 | 1984-07-10 | Phillips Petroleum Company | Passivating metals on cracking catalysts |
US4585628A (en) * | 1983-04-01 | 1986-04-29 | American Cyanamid Company | Stripping metals from spent catalysts |
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